Silver halide photosensitive material

ABSTRACT

An improved silver halide photosensitive material is disclosed which comprises, as a high boiling point solvent for photographic additives such as couplers, at least one solvent selected from (1) straight or cyclic alkanes having at least 9 carbon atoms, (2) straight or cyclic alkenes having at least 9 carbon atoms, and (3) compounds represented by the following general formula:   WHEREIN R1, R2 and R3 are individually hydrogen, alkyl, cycloalkyl or aryloxy, or R1 and R2 can cooperatively form a hydrocarbon ring as members thereof.

United States Patent 1 Nakajima et al.

[ 1 Oct. 14, 1975 SILVER HALIDE PHOTOSENSITIVE MATERIAL [73] Assignee: Konishiroku Photo Industry Co.,

Ltd., Tokyo, Japan 22 Filed: Dec. 19,1973

21 Appl. No.: 425,977

[30] Foreign Application Priority Data Dec. 28, 1972 Japan 47-130258 [52] US. Cl 96/84 R; 96/84 UV; 96/88;

[51] Int. Cl. G03C I/84; 603C l/4O [58] Field of Search 96/100, 84 UV [561 References Cited UNITED STATES PATENTS 3,658,546 4/1972 Doorselaer et a1. 96/100 3,676,142 7/1972 Carpentier et al.... 96/100 3,752,672 8/1973 DePauw et al 96/100 3,788,857 l/l974 VanPoucke et al. 96/100 Primary Examiner-Ronald H. Smith Attorney, Agent, or FirmBierman & Bierman [57] ABSTRACT An improved silver halide photosensitive material is disclosed which comprises, as a high boiling point solvent for photographic additives such as couplers, at least one solvent selected from (1) straight or cyclic alkanes having at least 9 carbon atoms, (2) straight or cyclic alkenes having at least 9 carbon atoms, and (3) compounds represented by the following general formula:

wherein R R and R are individually hydrogen, alkyl, cycloalkyl or aryloxy, or R and R can cooperatively form a hydrocarbon ring as members thereof.

3 Claims, No Drawings SILVER HALIDE PHOTOSENSITIVE MATERIAL consisting of (1) compounds represented by the gen eral formula This invention relates to a photographic material characterized in that a photographic additive which is E usually added to a photographic material in the form dissolved in a high boiling point solvent, such as a ultraviolet absorber, a coupler and the like, is incorporated 2 3 in a photographic material with use of a novel photographic solvent.

As is well known in the art, ultraviolet absorbers of (wherein R R2 and R3 are respectively a hydrogen the behlophehohe yp the behzh'lazoletype1 the atom, alkyl, cycloalkyl, aryloxy, or R and R may form lohhrhe yp the trialihe type and of the cyahome' together a hydrocarbon ring,) (2) straight and cyclic thylehebehlodhhiol yp are employed as Ph alkanes having at least 9 carbon atoms and (3) straight g p ultravlolet absorbers and and cyclic alkenes having at least 9 carbon atoms. amiylhhehoxybutyl)4'hydroxy'z'haphthamlde of the '15 These high boiling point solvents may be used singly or followmg formula in the form of a mixture of two or more of them, It is also possible to employ these high boiling point sol- OH vents in combination with low boiling point solvents as in 1the case of conventt iolpal hitglhbbciiling point slolvents. ypica instances 0 t e hig oi ing oint so vent to C0NH(CH) OT Q csHm be used in this invention include cum ne, p-cymene, mesitylene, di-isopropyl benzene, n-butyl benzene, seccsHum butyl benzene, t-butyl benzene, hexyl benzene, cyclo- 5 hexyl benzene, dodecyl benzene, diphenyl ether, n-

decane, decalin, tetralin, l-dodecene, l-decene, and

l-nonene.

h Results of the test of the dissolving power of the solamylphehhxyhcetamldo benzamldo's'pyrazolone of vents made with use of a ultraviolet absorber as the adfollowlhg formula ditive to be dissolved are shown below.

TEST EXAMPLE fi O A mixture of four ultraviolet absorbers, 2-(2- hydroxy-S -tert-butylphenyl)benztriazole, 2-( 2 NHCOCHTOTQ'QHH) hydroxy-3'-tert-butyl-5'-di-tert-butylpenyl)benztiazole N and 2-( 2-hydroxy-3 5 -di-tert-butylphenyl)-5- l cHnm chlorobenztriazole was used as the ultraviolet absorber. C1 l lg of the above mixture was dissolved in 2ml of ethyl acetate and 1 ml of a high boiling point solvent indi- 0 cated below in Table l, and 20 ml of water was added I 4 to the solution.

The mixture was shaken and allowed to stand still. The time as which the ultraviolet absorber was precipitated was measured to obtain results shown in Table l.

and the like are employed for protected couplers. '45

These additives are usually added to a photographic Table 1 material in the state dissolved in a high boiling point I solvent such as di-n-butyl phthalate, triphenyl phosg 'j g f g ffig phate, tri-ocresyl phosphate, monophenyl-di-p-tert- 50mm Absorber Began butyl phosphate, monophenyl di-o-chlorophenyl phosphate tri-p-tert-butylphenyl phosphate di-p'tert' g lTe h i dibutyl phthalate within 3 hours butylphenyl-mono-( 5-tert-butyl-2-phenyl-phenyl) Solvent of decalin more than I69 hours phosphate and the like. This invfmivn However, these high boiling point solvents are still fg ii i g :8: $2: :2: insufficient in the dissolving power. mdodecane more than 168 hours For example, because of the insufficient dissolving power, the photographic additive is precipitated in the form of crystals at the step of coating a gelatin layer, As is seen from the results shown in Table l, the so]- and the presence of crystals of the photograph addi- 0 vent to be used in this invention has a much higher dishave h lhfluehces the P p of the coated solving power than the comparative solvent. Therefore, P F F P when a ultraviolet absorber is added to elemental sub- This invention is to provide a photographic material t stances of a photosensitive materlal in the form CllS- of good quality formed with use of a high boiling point 1 d th I t f d f solvent free of such defects involved in conventional 5 so m 6 so van 0 t l e F i high boiling point solvents ventional solvents as above mentioned are eliminated. I The high boiling point solvent to be used in this in- Further, when a Protected coupler is added to vention is at least one member selected from the group mental substances of a photographic material with use of the solvent of this invention, there can be obtained an excellent photographic material in which photographic properties are not damaged for a long period of time.

The solvent to be used in this invention is photographically harmless and has no bad influences on other photographic additives.

This invention will now be illustrated more detailedly by reference to examples.

EXAMPLE 1 A photosensitive silver chlorobromide gelatin emulsion for red sensitive containing a cyan coupler was coated on a raw paper for photographic use, and a gelatin solution containing a solution of the same ultraviolet absorber as used in Test Example which was prepared with use of a high boiling point solvent indicated in Table 2 was coated on the emulsion layer so that a protective gelatin layer was formed at a base weight of 6.0 mg/ 10 cm Then, the coated gelatin layer was dried to obtain a test sample.

The solution for formation of the gelatin protective layer was prepared by dissolving 3 g of the ultraviolet absorber in 6 ml of ethyl acetate and 3 ml of the high boiling point solvent, adding the solution to 60 ml of a 10% aqueous solution of gelatin containing saponin,

emulsifying and dispersing the mixed solution by means of a colloid mill and adding ml of water to the dispersed solution.

The so obtained sample was exposed to light, subjected to color development, hardening fixation, bleaching fixation and water washing, and then dried. 3

With respect to each sample, the red density of the cyan image and stain density (determined based on the blue color concentration) at non-image areas were measured. Then, the sample was exposed directly to 40 sun-light for hours while employing a blue scale as a comparison, and the red density and stain density were measured again. Results of the reduction ratio of the red density and the stain density are shown in Table Table 2 Reduction Ratio of Red Color Density (density Stain Density As is seen from the results shown in Table l, the protective gelatin layer containing a solvent according to this invention exhibits fading preventive effect and stain preventive effect substantially equal to these of a gelatin protective layer containing a solvent of difutyl phthalate.

On the other hand, the solution comprising photographic additives and the solvent according to this invention exhibited more stability than the solution comprising photographic additives and the dibutyl phthalate, that is, crystalization did not occured on and before coating at all. When as ultraviolet absorber, 4,7- bis(,B-ethoxyethoxy corbonylmethoxy)-2- dicyanomethylene-l,3-benzodithiole was used instead of a mixture of four kinds of benztriazole, supreme results are also obtained as same as the above.

EXAMPLE 2 v 20 mg of l-(2,4,6-trichlorophenyl)-3-[-3-{(2,4-ditert-amylphenoxy)-acetamidelbenzamide1-5- pyrazolone was dissolved in 20 ml of l-nonene and ml of ethyl acetate (maintained at 60C), and the-solution was mixed with 10 ml of a 10% aqueous solution of Alkanol B and 200 m of a 5 aqueous solution of gelatin. The mixture was emulsified and dispersed by means of a colloid mill.

The so obtained dispersion was added to 1 Kg of a.'silver chlorobromide emulsion for formation of photographic papers, and the mixture was coated on a raw papers, and dried. The so obtained sample was exposed to green light exposure, subjected to color development hardening fixation, bleaching fixation and water washing, and dried. As a result, there was obtained an image of a magenta color comparable to the image obtained by employing dibutyl phthalate instead of lnonene.

What is claimed is: g

1. In a silver halide photosensitive material comprising a high boiling point solvent for photographic additives, the improvement which comprises said solvent being selected from a group consisting of straight or cyclic, alkanes and alkenes having at least 9 carbon atoms; and cumene, p-cymene, mesitylene, diisopropyl benzene, n-butyl benzene, sec-butyl benzene, t-butyl benzene, hexyl benzene, cyclohexyl benzene, dodecyl benzene and dephenyl ether.

2. A silver halide photosensitive material according to claim 1 wherein said photographic additives are couplers.

3. A silver halide photosensitive material according to claim 1 wherein said photographic additives are ultraviolet absorbers. 

1. IN A SILVER HALIDE PHOTOSENSITIVE MATERIAL COMPRISING A HIGH BOILING POINT SOLVENT FOR PHOTOGRAPHIC ADDITIVES, THE IMPROVEMENT WHICH COMPRISES SAID SOLVENT BEING SELECTED FROM A GROUP CONSISTING OF STRAIGHT OR CYCLIC, ALKANES AND ALKENES HAVING AT LEAST 9 CARBON ATOMS, AND CUMENE, PCYMENE, MESITYLENE, DI-ISOPROPYL BENZENE, N-BUTYL BENZENE, SEC-BUTYL BENZENE, T-BUTYL BENZENE, HEXYL BENZENE, CYCLOHEXYL BENZENE, DODECYL BENZENE AND DEPHENYL ETHER.
 2. A silver halide photosensitive material according to claim 1 wherein said photographic additives are couplers.
 3. A silver halide photosensitive material according to claim 1 wherein said photographic additives are ultraviolet absorbers. 